Light-sensitive silver halide color photographic materials containing cyan coupler

ABSTRACT

A coupler having the formula   WHEREIN R is an aryl or aralkyl group or unsaturated aliphatic hydrocarbon residue having one to 22 carbon atoms, R&#39;&#39; is an aliphatic residue having one to six carbon atoms, and X is hydrogen or halogen is incorporated within a light-sensitive silver halide color photographic emulsion. A composition useful for forming a cyan-colored photographic image is produced. Deposition of the coupler in the emulsion is substantially reduced. The color formation rate of the coupler is close to that of other magenta and yellow couplers. This enables the three colors to be readily balanced in speed. A finely grained color image is obtained upon color development.

United States Patent lwama et al.

541 LXGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIALS CONTAINING CYAN COUPLER [72] Inventors: Masakuni lwama; Toshihiko Yamamoto;

Keiii Kasai; Yoshinobu Nakagawa; Takaya Endo, all of Tokyo, Japan [73] Assignee: Konishiroku Photo Industry Co., Ltd.

[22] Filed: July 13, 1970 [21] App]. No.: 54,625

[30] Foreign Application Priority Data July 16, 1969 Japan ..44/55733 [52] U.S. Cl ..96/100, 96/9 [51] Int. Cl

[58] Field ofSearch ..96/55,100

[56] References Cited UNITED STATES PATENTS 2,186,850 1/1940 Wilmanns et a1. ..96/100 2,476,559 7/1949 Nawiasky et al ..96/100 2,860,974 11/1958 Williams... ..96/100 3,271,152 9/1966 Hanson ..96/100 Primary Examiner-.l. Travis Brown Att0rneyHarry C. Bierman, Jordan B. Bierman and Bierman & Bierman Mar. 14, 1972 wherein R is an aryl or aralkyl group or unsaturated aliphatic hydrocarbon residue having one to 22 carbon atoms, R is an aliphatic residue having one tosix carbon atoms, and

hydrogen onhalogen is incorporated within alight-sensitive silver halide color photographic emulsion. A composition useful for forming a cyan-colored photographic image is produced. Deposition of the coupler in the emulsion is substantially reduced. The color formation rate of the coupler is close to that of other magenta and yellow couplers. This enables the three colors to be readily balanced in speed. A finely grained color image is obtained upon color development.

2 Claims, No Drawings LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPI-IIC MATERIALS CONTAINING CYAN COUPLER The present invention relates to a light-sensitive color photographic material incorporated with a novel coupler for forming a cyan-colored photographic image.

For the formation of a color photographic image according to the conventional subtractive color photography, there have been used, in general, couplers capable of coupling with an oxide of the N,N-disubstituted p-phenylene-diamine-type developing agent to form yellow, cyan and magenta colors. Particularly in the case of the so-called internal color photography in which said couplers are incorporated into photographic emulsions to form the colors, there are two processes; a process in which water-solubilizing groups (e.g., SO H and COOI-I groups) are introduced into the molecules of the couplers, the thus treated couplers are dissolved in alkali solution or the like and the resulting solutions are added to the emulsions, and a process in which the couplers are made oi]- soluble by introducing oil-solubilizing groups (e.g., higher alkyl groups) into the molecules thereof and dissolved in various organic solvents (e.g., di-n-butyl phthalate and the like), and the resulting solutions are added to the emulsions.

It is needless to say that color images obtained by color development are desired to be favorable in color reproductivity, excellent in color tone and high in stability to light, heat and temperature. In this respect, it has been said to be desirable to use so-called protect-type couplers which are water-insoluble or difficulty water-soluble and which can be dissolved in organic solvents and dispersed in photographic emulsions. Particularly important conditions in the case where said protect-type couplers are used are such that the couplers should have sufficient solubilities for organic solvents (hereinafter referred to as coupler solvents" and should not deposit or agglomerate even when dispersed in photographic emulsions and even after coated as light-sensitive materials on supports. In view of the above, many oleophilic components have chiefly been examined and studies on the synthesis of various derivatives have been made. However, most of the couplers obtained do not show sufficient solubilities for the coupler solvents, or are insufficient in dispersibility in photographic emulsions and deposit when added to the emulsions or after being coated on supports. Further, cyan couplers are higher, in general, in color formation rate than magenta and yellow couplers, and therefore the resulting color images are not well balanced in density, in most cases. In order to make the balance in density of color image more favorable, there have been made many such attempts that the speed of red-sensitive layer is decreased or the speeds of greenand blue-sensitive layers are increased.

An object ofthe present invention is to provide a light-sensitive photographic material incorporated with a cyan coupler, which shows sufficient solubility for a coupler solvent, e.g., din-butyl phthalate, o-tricresyl phosphate, di-n-butyl lauramide or ethyl acetate and which does not deposit or agglomerate after the coupler dispersion has been dispersed in a photographic emulsion or after the coupler-incorporated emulsion has been coated on a support.

Another object of the invention is to provide a novel coupler, which can inhibit the color formation rate of naphtholtype cyan coupler to obtain the balance of 3 layers and, at the same time, can have a dye formed in fine grain state by color development.

Conventional cyan couplers, e.g., l-hydroxy-2-naphthamide type derivatives of the formula,

CONHR X wherein R is a higher alkyl group, and X is a hydrogen or halogen atom, are excellent in formation efiiciency of indoaniline dye images obtained by coupling with oxidation products of N,N -disubstituted p-phenylenediamine type developing agents, and have excellent color tones. However, the conventional couplers have many such practical drawbacks that they are inferior in solubility for coupler solvents and severely deposit in photographic emulsions, and most of the particles of the formed dyes are coarse.

As an attempt to increase the solubility for coupler solvents, Japanese Pat. Publication No. 11,303/1967 proposes the use of couplers represented by the formula (II) in which has been formed such an oxazine ring as shown below.

wherein R is a saturated hydrocarbon, and X is a hydrogen or halogen atom.

However, the couplers of this kind are extremely low in coupling rate at the time of color development and hence are substantially impractical, though they have somewhat been improved in solubility.

In view of the above, we have made various studies to find couplers represented by the general formula (III) shown below which are free from such drawbacks as seen in the couplers of the general formulas (I) and (II) and which can sufficiently satisfy the objects of the present invention.

o (6 (III) 0- |COR CONHR wherein R is a substituted aryl or aralkyl group or a saturated or unsaturated and substituted or unsubstituted aliphatic hydrocarbon residue having one to 22 carbon atoms; R is an aliphatic hydrocarbon residue having one to six carbon atoms; and X is a hydrogen or halogen atom.

The alkoxalyl-type cyan couplers represented by the abovementioned general formula have increased solubilities for coupler solvents. Particularly, those of the said general formula (III), in which R is an aliphatic hydrocarbon residue having four to six carbon atoms, could be easily dissolved in coupler solvents of one-half to one-third of the amounts required in the case of corresponding couplers represented by the general formula (I), and, even when the solutions were allowed to stand at room temperature, they were extremely long in time required for initiation of deposition. Further, they showed improved oil solubilities. The solubility test was carried out in such a manner that l g. of a coupler of the present invention was dissolved in di-n-butyl phthalate over a water bath at 60 C., and the resulting solution was allowed to stand at 20 C. to observe the crystallization initiation time of the coupler. The properties of corresponding couplers of the general formula (I) were also measured at the same time and compared with those of the present couplers. The present couplers in which R=C were substantially identical in solubility with the couplers of the general formula (I), but those in which R'=C. I I were considerably improved both in solubility and in deposition characteristic, as shown in the following table.

Control coupler Present coupler R=H O Amount Deposition Amount Deposition of coupler initiation of coupler initiation solvent time solvent time (|)R 10ml 5hrs 5m] Thrs. OCONHCmHa:

OR 1 ml No deposition." 1 rnl No deposition. @[joorvncmm R ml 5 hrs 5 ml No deposition.

CONH(CH;)4O-C5 MU l C5Hn( (])E 101111 60min 5rnl ZOhrs.

C O NH 015113: (11) As seen in the above table, the couplers prepared by chang- 0H w m mg the hydroxyl groups of the couplers of the general l formula (I) to CONHCHH Ii ll l ooon' 11 NH: 6

CONHCmH V V V V l 7 are increased in solubility for coupler solvents to make it d Jolor t possible to obtain coupler solutions of high concentration. 0 g opmen I hi i n or allowed to stand. the cr stall iven when these so to s e y g g N lization of the couplers lS extremely slow. I

Further, when the photographic emulsion having the 0NHOnHn present coupler dispersed therein is coated on a support, the amount of high boiling solvent per unit area is small, and therefore the emulsion is less afiected by the high boiling 501- I vent and can be easily formed into a thin layer to give such ad- N vantage that the resulting color image is improved in sharp- 4 ness Coupler used 5 5 Formed dye The present coupler of the general formula (III) is somewhat lower in color formation rate than a corresponding coupler of the general formula (I). This, however, results in such advantage that the coupler becomes close in color formation rate to other magenta and yellow couplers, with the result that the 3 colors can easily be balanced in speed.

Further, in the case of the present coupler, the dye formed by color development becomes finer in grain size than in the case of a corresponding coupler of the general formula (I) to make it possible to obtain a color image with extremely fine grains.

In addition to the above-mentioned advantages, the coupler of the present invention has such important significance as set forth below.

That is, even when the OH group in the l-position is changed to such an alkoxalyloxy group as seen in the general formula (III), the coupler is not hindered in function and, moreover, the alkoxalyl group in' the l-position is removed during the step of color development to form the same dye as that formed from a corresponding coupler of the general formula (I), as shown below, for example.

Examples of the coupler compounds represented by the general Formula (III) which are used in the present invention are as shown below, but these are, of course,

not limitative.

w a m w w 6 O nw C o c Oil T U s P U m) M m m .m e h t f 0 no an mH dw r t 5 4 m H a. G H N O C CiHn (CH2)nNHC O 0 CH M I-O 02115 f c ONHCnHMn) wherein n is an integer of l to 64 These compounds can easily be synthesized by reacting corresponding l-hydroxy-Z-naphthamide type couplers with al- CONHCm -zKH) koxaryl chlorides in xylene or acetonitrile.

Synthesis examples of typical couplers are set forth below. Synthesis Example ll V Synthesis of ethoxalyl chloride 25.3 g. of oxalyl chloride was charged into a three-necked flask. Into this was dropped with stirring 9.2 g. of ethanol over a period of 1 hour while maintaining the inner temperature at below 10 C. The resulting mixture was reacted with stirring at room temperature for 30 minutes and then subjected to distilwas stirred at below 20 C. for 1 hour and at room temperature for additional 1 hour. Subsequently, the pyridine and acetonitrile were removed by means of an aspirator, and the residue was poured into 150 ml. of ice water to precipitate a lation to obtain 18.3 of ethoxalyl chloride, yield 69 percent, 5 ale yellow oil. The oil was extracted from 100 ml. of ethyl -P 4 "136 C-, n 1-4170 acetate, washed with water and concentrated under reduced synthesls Example pressure. The concentrate was recrystallized from 50 ml. of n- Synthesis ofbuwxalyl chloride hexane to obtain 2.5 g. of white needlelike crystals, yield 56 Synthesls Example 1 was repeated. except g of percent, m.p. 98-99 C. According to infrared analysis, the [911131101 E Place Of the ethanol. to Obtam gof a lo crystals showed characteristic absorptions at 1,760 cm. and colorless liquid, yield 68 percent, b.p. 73-75 C./8 mmJ-lg, 14550011714 2 Synthesis Example Vll Symhesls Example In Synthesis of l-ethoxalyloxy-N-(n-dodecyl)-4-chloro-2- Synthesis of l-ethoxalyloxy-N-[w-(2,4-di-tert-amylphenoxnaphthamlde (EXemPllfied Compound y) butyl]-2-naphthamide (Exemplified compound 6): N-n-dodecyl-l-hydroxy-4-chloro-Z-naphthamide was A mixture comprising 4.7 g. of 1-hydroxy-N-[w-(2,4-di-t treated in the same manner as in Synthesis Example V1 to obamylphenoxy) butyl]-2-naphtharnide, 25 ml. of pyridine and tain white needlelike crystals, yield 72 percent, m.p. 97-98 15 ml. of acetonitrile was charged into a 50 ml. three-necked flask. To the flask were attached a stirrer, a thermometer and Synthesis Example Vlll a dropping funnel. Further, a calcium chloride tube was at Syn of lx lyl xy- -(ny ltached for desiccation. Into the flask was dropped 2.6 g. of naphlhamide (EXemPlified Compound ethoxalyl chloride over a period of 40 minutes, while main- Synthesis Example V] was repeated, except that butoxalyl taining the inner temperature at 5 C. i 2 C. After stirring the chloride and N-n-dodecyl-l -hydroxy-4chloro-Znaphthamide resulting mixture at below 10 C. for 1 hour and at room temwere used in place of the ethoxalyl chloride and N-n-dodecylperature for additional l hour, the pyridine and acetonitrile l-hydroxy 2naphthamide, to obtain white needlelike crystals, were removed by means of an aspirator, and the residue was yield 88 percent, m.p. 8889 C. poured into 150 ml. of ice water. The resulting pale yellow oil Synthesis Example [X was extracted from 100 ml. of ethyl acetate, washed with Synthesis of l-ethoxalyloxy-N-n-dodecyl-4-iodo-2naphthawater and then concentrated under reduced pressure. The mide (Exemplified compound 10): concentrate was recrystallized from 50 ml. of n-hexane to 0b- Synthesis Example Vl was repeated, except that N-ntaln 3.0 g. of white sand-like crystals, yield 54.5 percent, m.p. d decyl-l-hydroxy-4-iodo-2-naphthamide was used in place 123L126) of the N-n-dodecyll -hydroxy-2-naphthamide, to obtain white Synthesis Example IV needlelike crystals, yield 69.0 percent, m.p. 68-69 c.

Synthesis of l-ethoxalyloxy-N-[w-(2,4-di-tert-amylphenox- Synthesis E p X y) butyl]-4-chloro-2-naphthamide (Exemplified compound Synthesis of y y yy P 13 mide (Exemplified compound 3):

1 2 4- 1-4. Synthesis Example VI was repeated, except that N-n-o cchloro-Z-naphthamide was treated in the same manner as in mdecyl-lhydroxy-z'naphthamlde and xylem Were used Synthesis Example 111 to obtain white sand-like crystals, yield 40 Place of the yy y yp a and 55 percent mp. 122 123 acetonitrile, to obtain white needlehke crystals, yield 85 per- Synthesis Example V r Synthesis of l-butoxalyloxy-N-lw-(2,4-di-tert-amylphenox- Synthesls Example XI y) bmylpzmaphthamide (Exempfifled compound 7): Synthesis of l-ethozalyloxy-N-(octadecenyl) 2-naphtha- Synthesis Example [11 was repeated, except that rr-butoxalyl (lixempllfied Q 5 )3 chloride was used in place of the ethoxalyl chloride, to obtain A mlxmfe compnsmg of X whim sandmke crystals yieid 55 percent mp. naphthamlde, 13 ml. of pyridine and 15 ml. ofacetonltrlle was symhesis Example v charged into a ml. three-necked flask. To the flask were at- Synthesis of 1-ethoxalyloxy-N-(n-dodccyl)-2-naphthamide tached a stiffen lhrfrmometer and a PP s f (E lifi d compound 1 50 Further, a calcium chloride tube was attached for desiccation. A mixture comprising 16 f N-n-dodecyl l-hyd oxy-z The inner temperature of the flask was maintained at 5 C. naphthamide, 25ml. of pyridine and 15 ml. of acetonitrile was and g- 0f hox lyl chloride was g adually dropped charged into a 50 ml. three-necked flask. To the flask were atinto the flask with stirring. Thereafter, the same operation as tached a stirrer, a thermometer and a dropping funnel. in Synthesis Example VI was effected to obtain 3.6 of a butter- Further, a calcium chloride tube was attached for desiccation. like oily substance, yield 67 percent. According to infrared The inner temperature of the flask was lowered to 5 C. 1 2 analysis, the thus obtained substance showed a characteristic C., while stirring the mixture. Into the flask was dropped 2.7 g. absorption at 1,750 cm". of the ethoxalyl chloride synthesized in Synthesis Example I Melting points and elementary analysis values of typical O r H P 0f 40 n After the pp g. the miXIure couplers used in the present invention are shown in Table 1.

TABLE 1 7 Elementary analysis values Calculated Found Exemplified M.p. compound. C.) C H N Cl C H N Cl The present invention is illustrated in further detail below with reference to examples, but the examples are illustrative, and it is needless to say that the invention is not limited thereto.

EXAMPLE 1 l g. of the exemplified coupler compound 4 was completely dissolved at 60 C. in a mixed liquid comprising 10 ml. of din-butyl phthalate and 20 ml. of ethyl acetate. This solution was mixed with 10 ml. of a 10 percent aqueous solution of Alkanol B (trade name of Du Font) and 200 ml. of a 5 percent aqueous gelatine solution, and the resulting mixture was subjected to a colloid mill to form a dispersion. The dispersion was added to 1,000 ml. of a red-sensitive silver iodobromide photographic emulsion. which was then coated on a film base, followed by drying, to obtain a light-sensitive color photographic material.

The thus obtained film was exposed and then developed at 20 C. for minutes with a developer of the following composition:

N.N-Diethyl-p-phenylenediamine hydrochloride 2.0 g. Anhydrous sodium sulfite 2.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g. Water to make l 000 ml Subsequently, the film was subjected to stopping and fixing according to ordinary procedures, washed with water for 10 to minutes and then treated for 5 minutes with a bleaching solution of the following composition:

Red prussiate I00 5. Potassium bromide 50 g. Water to make 1,000 ml.

The film was further washed with water for 5 minutes and then fixed for 5 minutes with the following fixing bath:

Sodium thiosulfare (pentahydrale) Water to make 250 g. 1,000 ml.

Thereafter, the film was washed with water and then dried. The thus treated film was excellent in transparency and had a cyan color image of fine grains having an absorption maxirnum at 690 Photographic properties of films obtained in the same manner as in Example 1, except that in place of the exemplified compound 4, there were used either singly or in combination the compounds A and B shown below which corresponded to the general formulas (l) and (III), respectively, are as shown in Table 2.

As is clear from Table 2, it is understood that as compared with the film prepared by use of the compound A, the film prepared by use of the present compound B is low in gamma value and the graininess of a color image obtained by printing the said film is excellent. This shows the fact that the coupler of the present invention is useful for obtaining three wellbalanced layers and for improving the graininess of the resulting image. When the couplers are used in admixture, no deposition of the couplers is observed, and therefore it is possible to obtain a color image excellent in transparency. In case the coupler matrix is same, as shown in Table 2, a same dye is formed and the calculation of color balance is easy. Furthermore, such coupler is advantageously low in cost.

The coupler of the present invention may be used in combination with such a cyan color coupler as represented by the general formula (IV) shown below, e.g., such color coupler for obtaining a color retouching mask as exemplified in U.S. Pat. No. 3,034,892, or in combination with the couplers of the general formulas (l) and (IV), whereby the deposition characteristic of the coupler and the graininess of the resulting image can be improved. The coupler of the general formula (IV) is indicated below:

wherein R and R individually are alkyl, aryl, aralkyl or acyl group. At the same time, the coupler can be so controlled as to attain adequate masking effects. Thus, the coupler of the present invention is an extremely useful cyan coupler.

EXAMPLE 2 EXAMPLE 3 15 g. of the exemplified coupler compound l was completely dissolved at 60 C. in a mixed liquid comprising 15 ml. of tricresyl phosphate and 45 ml. of butyl acetate. This solution was mixed with 8 ml. ofa 10 percent aqueous solution of Alkanol B and 300 ml. ofa 5 percent aqueous gelatine solution, and the resulting mixture was subjected to a colloid mill to form a dispersion. The dispersion was added to 1,000 ml. of a red-sensitive gelatino silver iodobromide photographic emulsion, which was then coated on a film base, followed by drymg.

The thus obtained film was exposed and then developed at 20 C. for 10 minutes with a developer of the following composition:

Metol 3.0 g. Anhydrous sodium sulfite 60.0 g. Hydroquinone 6.0 g. Anhydrous sodium carbonate 50.0 g. Potassium bromide l.0 g. Water to make L000 ml.

Subsequently, the film was subjected to ordinary stopping and hardening treatments and water-washing. The thus treated film was further subjected to secondary exposure by use of a white light and then developed at 20 C. for 12 minutes with a developer of the following composition:

N.N-Diethyl-p-phenylenediarnine 5.0 g. Anhydrous sodium sulfite 2.0 g. Sodium carbonate (monohydratc) 82.0 g. Potassium bromide 1.0 g. Water to make 1.000 ml.

The developed film was stopped, fixed, water-washed and bleached according to ordinary procedures and then washed with running water for 20 minutes, followed by drying, to obtain a positive cyan color image of fine grains having an absorption maximum at 689 ,u and excellent in transparency.

EXAMPLE 4 lOO g. of the exemplified coupler compound 12 was completely dissolved at 60 C. in 100 ml. of di-n-butyl phthalate. This solution was added to 5 liters of a percent aqueous gelatine solution kept at 60 C., and further charged with 200 ml. of a 10 percent aqueous sodium alkylbenzenesulfonate solution. The resulting mixture was subjected to a colloid mill at about 60 C. for 10 minutes to form a dispersion. The dispersion was stirred for 10 minutes. This operation was repeated four times with intervals of 1 minute to obtain a coupler dispersion. The thus obtained dispersion was added to 10 liters of a gelatino silver iodobromide emulsion containing a red-sensitive sensitizing dye. After thorough stirring, the emulsion was coated on a film support at 30 to 35 C. and then dried to prepare a light-sensitive color photographic material.

This film was exposed and then color-developed, bleached and fixed in the same manner as in Example 1 to obtain a cyan-colored negative image.

The film prepared by use of the exemplified coupler compound 13 was quite excellent in transparency and showed an absorption maximum at 690 u.

EXAMPLE 5 7 g. of the exemplified coupler compound 12 and 3 g. of N- n-dodecyl-l-hydroxy-4-chloro-2-naphthamide, a coupler corresponding to the general formula (I) were completely dis solved at 60 C. in a mixed liquid comprising 7 ml. of cli-nbutyl phthalate and 15 ml. of ethyl acetate. This solution was mixed with 10 ml. of a 10 percent aqueous solution of Alkanol B and 200 ml. of a 5 percent aqueous gelatine solution. The resulting mixture was subjected to a colloid mill to form a dispersion. The dispersion was added to 1,000 ml. of a redsensitive silver iodobromide emulsion, which was then coated on a film base, followed by drying to prepare a light-sensitive photographic material.

This film was exposed according to an ordinary procedure and then treated with the same developer as in Example 2 to obtain a cyan color image of fine grains which was excellent in transparency.

What is claimed is:

l. A light-sensitive silver halide color photographic emulsion incorporated with a coupler of the general formula.

CONHR wherein R is an aryl or aralkyl group or a saturated or unsaturated, aliphatic hydrocarbon residue having one to 22 carbon atoms; R is an aliphatic hydrocarbon residue having one to six carbon atoms; and X is a hydrogen or halogen atom.

2. A light-sensitive silver halide color photographic element which comprises a support and, coated thereon, a light-sensitive silver halide color photographic emulsion as claimed in claim 1. 

2. A light-sensitive silver halide color photographic element which comprises a support and, coated thereon, a light-sensitive silver halide color photographic emulsion as claimed in claim
 1. 